Aliphatic esters of 2,4,5-trichlorophenol



CZZZA XR "294579805 g lratflnted Jan. l

I tion ofNew Jersey No Drawing.

-"I'his "invention relates to new chemical sub- Application November 2,l946, SerialNo.707,520 2.1

4 Claims. (onst ge stances,'- and more especially toeslifimzelitrichlorophenol and aliphatic acids having not more than-l2 carbon atoms.

-The novel esters may be obtained by reacting 2,4,5-trichlorophenol anda suitable acid anhydride or acid chloride in the presence of an inert solvent such asbenzene or toluene, the desired characteristic odor which is'not regarded as beester being then isolated'by distillation-or crystallization.

' In general, the novel esters are colorless crystalline solids. soma'howeverfare liquids. They are soluble in-many common organic solvents,

such as acetone, ethyl acetate; toluene and naphtha, but are only slightly soluble in ethyl alcohol, and insoluble in water. 1

Our esters possess the very unexpected property of being effective fungicides when used for the protection of wool and leather against the attack of fungi of the-species Pencillium and Aspergillus,

and for the treatment of cottonseed against infection by C. gossypii.

ESTER-S or 2,4,5.

.rn omonornnnor. p v K Arthur' 'R. 'oad, Rutherford. and. William s..

Gump, Upper Mcntclair, N. J assignors to Burton T. Bush, 1110., New York, N. Y., a corporasubject to transmit restrictions, making another reason for desiring non-mercury fungicides One of the non-mercury fungicides hitherto developed is 2,4,5-trichlorophenol. A substantial part of its fungicidal activity has been attributed to the phenolic hydroxyl group it contains. The disadvantages of the 2,4,5-trichlorophenol are that it is irritating and it has a rather strong,

ing an agreeable one. g Y

The novel esters hereindo not possess the dis advantages ,of the free, phenol. They do possess considerable fungicidal activity.v This is .very surprising in View oi the fact that the hydroxyl groupof the 2,4,5-trichlorophenol has .been blocked and doesnot exist in the esters. 1

Inorder more fully to clarify this invention the following examples are given by way of illustra- That the foregoing named property was quite unexpected may be seen from a consideration of the following. It has long been known that cottonseeds, like the majority of seeds, carry spores of certain fungi. After planting the seeds, these spores often germinate,- thereby rendering the plant subject "to attack-by the resulting fungbus growth and often terminating inthe death of the plant. Sometimes, the plant does not'live to breakthrough the ground. Bethisas'itmay,

the inevitable result is that there is a large economic loss to the nation, in the 'form'of poor yields of cotton per acre ofseed planted.

/Natur'ally, such a condition attracted efiorts to ameliorate it;- -.As".a result, several. methods tion. V.

E AMPLE I I Formate of 2,4,5-trichlorophenol (Ill '172 grams of acetic anhydride were cooled to 15 C. and under stirring 40 grams of formic acid were added at such a rate that the temperature did not exceed 20 C. A solution of'llO grams of 2,4,5-trichlorophenol in grams of formic acid had been prepared by heating and serious objection, as some of the materials employed actually attack the seed itselfvand incorrect application of the material may cause re:- duction ingermination. 4-1;; Moreover, manypof" the most. successful compounds-are thoseinvolving' theuse'of mercury salts. As is' well known, these. compounds. are poisonous... All too often there are reports that the. paste obtained on C001il'lg of the solution was added slowly to the acetic anhydride-formic acid mixture during one hour. The clear reaction mixture was allowed to stand at room temperature '(about 25 C.) for five days. After that period, crystals had formed which were filtered oflf, washed with 50% aqueous formic acid, and water, and dried in vacuo. 82 grams of 2,4,5- trichlorophenyl formate, as white needles, melting at 72 C.-73 C., were obtained.

The 2,4,5-trichlorophenyl for-mate exhibited fungicidal properties when tested on wool and leather against Aspergillus and Penicilliu'm spores. Two methods of test were employed: the zone of inhibition test and the moist chamber method. In the first test, the wool and leather were soaked in a 2% alcoholic solution of the formate. The alcohol was evaporated by air-drying. --The culture medium used for this test was prepared according-to the formula given in Specification 3 No. T 1212A, of the U. S. Army Corps Of Engineers, and consisted of Sucrose 30500 Agar 15.60 Water, to make volume of 160;) cc.

Petri dishes were prepared containing; cc.

of the medium. Some dishes were inoccu-latied'" with Aspergillus spores and some with Penicil isms.

- The treated wool and leather samples, as well as untreated samples, were placed on topoi. the. 155

agar, and the plates were incubated in awaits C. for a period of 12. to 14 days. were observed for the presence of any clear zone around the sample and also for the presence ef any fungi growing on the surface of the earn 2 ples. 1

It was'found' that: the treatedsampleswere free of'fungi and were-surrounded by aicl'ea-r zone; whereas; the untreated samples had numerous fungi thereon and no zone of inhibition around the samples. w

The other test involvedpreparingsamples-0t wool and leather as before and thenhanging them vertically in a closed moist chamber'f'or a month. i The treated samples-were found free ofi fungi but the untreated samples hadheedat tacked severely by the fungi. "Theformate Wastested on cottonsee found to give protection against (l yossy-pit; "Cot"- tonseed treated with the formate gives high yields ofcotton.

EX-AMPLE II Acetate of 2,4,5 trz'chZo1'ophenol melting point 67 C.68C.,.Wereobtaihedn.

The acetate, when tested as, the, formate was tested in accordance. with Example I',. alsoexhibited' fungicidal propertiesv EXAMPLEIII' Y H Propionate of; 2,4,5-trichlorozihenol I 100 grams of 2,4,5-trichlor0phenol were?- refluxed for 6 hours with 200' grams or propionio anhydride. After cooling; the mixture was-poured on. ice and allowed to stand over-night. The'oil wasextracted. with benzene; the: benzene; solution Thewet solid; was

4 washed with water, then sodium bicarbonate solution, and again with Water, and dried with anhydrous sodium sulfate. After removal of the benzene, the residual oil was distilled at a pressure of 5 mm. of mercury. grams, boiling at 53'C.-110 C. were discarded; the second fraction. grams) boiling point C.- C. was redistilledfand (id-grams ofthe propionate, boiling point I23 6-130 C. were" obtained. The liquid, dza, =1.39O2, n =1.5418, congealed after a few days standing to a solid, C. P. 38 C. 'fihe propionate, when tested as the formate -'.w'a.s;'tested in accordance with Example I, also I ,vexhi'bited fungicidal properties. 1mm spores, by swabbmg the surfaceof the agar v 1 solution with a water suspension of theergarre .2, i,5-trichlorophenol 90 grams); was. dissolved M300 cc. of benzene under heating and stirring; 7.0- gramsof II-CaPYOYI- chloride were drownedv in during 2 hours and the mixture refluxed for 5 hours. After cooling, 200 co. more of benzene were added and the benzene solution twice washed with water and. dried with anhydrous sodium sulfate. A smallamount of isopropanol had. been added to clear the solution. The solvent was removed by distillation and the residual oil distilled ata pressure of 41 mm. of mercury. 107. grams; of 2,4;5 trichlorophenyln-canroatewere obtained. The liquid,- d25 =l.2691, n =l-.525Q, boiled at 1.66 C. B t-4: mm. of mercury. H The n-caproate, when tested as. the formate was tested in accordance with Example also exhibitedfungicidalproperties. v

li; v EXKMPLEV,

z Isocaptoateor 2,.4,5-tziehlorophencl 'Th'e 2,4;5-trichloronlienyl-isocaproate was ob tamed-ma. similar manner as the. n-caproate, using. iso-caproylchloride. The iso-caproate is a liquid, boiling. point-170 c. 172 C..d25 =-1.274.0, n =1.5-2.66. I

The-iso -ca-proate, when tested as the formate was. tested in accordance with Example-L; also exhibited fungicidal properties.

EXAMPLE VI 5 6 The laurate, when tested as the formate was consisting of H and an alkyl radical containing tested in accordance with Example I, also exnot more than eleven carbon atoms. hibited fungicidal properties. 2. The formate of 2,4,5-trich10r09hen0l. The foregoing illustrates the practice of this 3. The acetate of 2,4,5-trichlorophenol.

invention, which however, is not to be limited 5 4. The propionate of 2,4,5-trichlorophenol. thereby but is to be construed as broadly as permissible in view of the prior art and limited solely ARTHUR R. CADE. by the appended claims. WILLIAM S. GUMP.

We claim: 1. Novel chemical compounds having the struc- 10 REFERENCES CITED tum! formula: The following references are of record in the file of this patent:

F Holleman et a1., Rec. trav. Chim., vol. 39

01 f (1920) page 738. o 15 Auwers et al., Ann. der Chem, [01,464 (1928) 1 page 310. wherein R is a member selected from the group z i a t s. 

